EP0139135B1 - Dérivés d'alkyl-4-imidazole, leur préparation et leur application - Google Patents

Dérivés d'alkyl-4-imidazole, leur préparation et leur application Download PDF

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Publication number
EP0139135B1
EP0139135B1 EP84109603A EP84109603A EP0139135B1 EP 0139135 B1 EP0139135 B1 EP 0139135B1 EP 84109603 A EP84109603 A EP 84109603A EP 84109603 A EP84109603 A EP 84109603A EP 0139135 B1 EP0139135 B1 EP 0139135B1
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EP
European Patent Office
Prior art keywords
formula
alkyl
methyl
compound
soil
Prior art date
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EP84109603A
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German (de)
English (en)
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EP0139135A1 (fr
Inventor
Toni Dr. Dockner
Ernst-Heinrich Dr. Pommer
Juergen Dr. Dipl.-Landwirt Dressel
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/68—Halogen atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S71/00—Chemistry: fertilizers
    • Y10S71/902—Nitrification inhibition

Definitions

  • the invention relates to new 4-alkylimidazole derivatives, their preparation and their use as nitrification inhibitors.
  • Ammonium nitrogen is oxidized in the soil by bacteria from the genera Nitrosomonas and Nitrobacter via nitrite nitrogen to nitrate nitrogen.
  • the extent of nitrification depends on the soil type, the pH value of the soil, the soil moisture and the biological activity of the soil. Since nitrate nitrogen, unlike ammonium nitrogen, is also subject to leaching, especially on lighter soils, and is therefore no longer available for plant nutrition and there is a risk of nitrate accumulation in the groundwater, nitrification inhibition is of particular importance.
  • R 1 preferably denotes a methyl group
  • R 2 preferably denotes a chlorine atom
  • R 3 preferably denotes the groups NR 5 R 6 , where R5 preferably denotes a hydrogen atom and R 6 preferably. represent a methyl group or a phenyl radical optionally substituted by up to 2 chlorine atoms.
  • the reaction a) is generally carried out in the presence of an equivalent amount of base.
  • bases are tertiary amines - such as trimethylamine or triethylamine - and alkali metal or alkaline earth metal hydroxides or alcoholates.
  • Suitable solvents are, for. B. chloroform, toluene, Xylene, chlorobenzenes.
  • the reaction usually succeeds at a temperature of 40 to 100 ° C. It is expedient to carry them out at the reflux temperature of the solvent used.
  • the reaction b) is carried out in a solvent which is inert under the reaction conditions.
  • a solvent which is inert under the reaction conditions.
  • Particularly suitable as such are hydrocarbons and halogenated hydrocarbons in the boiling range from 40 to 140 ° C., preferably 60 to 110 ° C., as well as acetonitrile and dimethylformamide.
  • the reaction usually takes place under reflux conditions.
  • the starting materials of the formula II required for the reactions can be obtained by reacting the corresponding imidazoles with halogen or hypohalite (cf. DE-OS 31 45 927).
  • the substances according to the invention can be used as such, i.e. H. as free (very weak) bases or as a salt of a biologically acceptable acid, preferably as phosphate, sulfate, acetate, citrate, tartrate, in particular as hydrochloride, alone or in a mixture with solid or liquid fertilizers which contain ammonium nitrogen, urea or ammonia will ; application together with plant treatment or soil conditioners is also possible.
  • the active ingredients are expediently applied simultaneously with the fertilizer.
  • the application rates are 0.05 to 10 kg / ha, preferably 0.5 to 3 kg / ha.
  • the active compounds can be used in amounts of 0.5 to 10 percent by weight, based on fertilizer nitrogen.
  • nitrification inhibitors according to the invention are very effective, non-toxic, non-volatile, sufficiently water-soluble and stable. They remain in the ground for a long time, so they remain effective for a long time. They are therefore not only used to protect the environment by preventing nitrate from being washed out into the groundwater. but also a significant improvement in fertilizer utilization, especially with lighter soils.
  • Example 2 Analogously to Example 1, 59.5 g of phenyl isocyanate were added dropwise to 58.5 g of 4-methyl-5-chloroimidazole in 250 ml of chloroform. The temperature rose to 42 ° C. The mixture was then refluxed for 2 hours and then cooled with ice. The precipitate was filtered off and washed with chloroform. After drying, 80 g (67.9%) of 1-N-phenylcarbamoyl-4-methyl-5-chlorimidazole, mp 112.3 to 114.4 ° C., were obtained.
  • Example 2 Analogously to Example 1, 29 g of 4-methyl-5-chloroimidazole and 47 g of 3,5-dichlorophenyl isocyanate, dissolved in 100 g of chloroform, were added dropwise. Then the mixture was boiled under reflux for 2 h, cooled and the residue was filtered off with suction. After washing with chloroform, the product was dried and 60 g (78.8%) of 1-N- (3,5-dichlorophenyl-carbamoyl) -4-methyl-5-chloroimidazole, mp. 136.9 to 138.6 ° C.
  • Example 2 Analogously to Example 1, 13 g of methyl isocyanate were added dropwise to 40 g of 4-methyl-5-bromimidazole in 200 g of chloroform. The temperature rose to 35 ° C. After boiling under reflux for 2 hours, the reaction solution was evaporated under reduced pressure. 55 g of residue were obtained, which was recrystallized from 110 ml of toluene. After the product had cooled and suctioned off, it was dried. 30 g (55%) of 1- [N-methyl-carbamoyl] -4-methyl-5-bromimidazole were obtained, mp. 98.4 to 100.1 ° C.
  • Example 2 Analogously to Example 1, 582.5 g of 4-methyl-5-chloroimidazole were dissolved in 1 500 ml of toluene at 70 ° C. 313.5 g of methyl isocyanate were slowly run into this solution. The temperature rose to about 90 ° C. The mixture was then refluxed for 30 minutes and then cooled. The mixture was stirred with ice cooling for 1 h and the precipitate which had separated out was filtered off with suction. It was washed with ether, dried and obtained 826 g (95.2%) of 1-N-methylcarbamoyl-4-methyl-5-chloroimidazole, mp. 95.6 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Fertilizers (AREA)

Claims (4)

1. Dérivés d'alkyl-4 imidazoles de la formule I
Figure imgb0014
dans laquelle
R1 désigne un radical alkyle en C1 à C4,
R2 désigne un atome de chlore ou de brome et
R3 désigne un groupe ―OR4 ou ―NR5R6, où R4 désigne un radical alkyle en C1 à C4, R5 un atome d'hydrogène ou un radical alkyle en C1 à C4 et R6 un radical alkyle en C1 à C4 ou un groupe phényle éventuellement mono- ou di-halo-substitué, ainsi que les sels de ces dérivés.
2. Procédé de préparation des composés de la formule I selon la revendication 1, caractérisé en ce que l'on fait réagir
a) lorsque R3 représente un groupe -OR4 ou -NR5R6 avec R5 = radical alkyle en C1 à C4 : un composé de la formule Il
Figure imgb0015
dans laquelle R1 et R2 possèdent la signification définie, en présence d'une base avec un composé de la formule III
Figure imgb0016
dans laquelle R3 possède la signification définie et X désigne un atome d'halogène ;
b) lorsque R3 représente un groupe ―NHR6 : un composé de la formule II dans un solvant avec un isocyanate de la formule IV
Figure imgb0017
dans laquelle R3 possède la signification définie.
3. Procédé pour inhiber la nitrification de l'azote ammoniacal dans le sol, caractérisé en ce que l'on incorpore au sol entre 0,05 et 10 kg d'un composé de la formule I selon la revendication 1 par hectare.
4. Inhibiteur de la nitrification, comprenant un composé de la formule I selon la revendication 1.
EP84109603A 1983-08-20 1984-08-13 Dérivés d'alkyl-4-imidazole, leur préparation et leur application Expired EP0139135B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84109603T ATE28192T1 (de) 1983-08-20 1984-08-13 4-alkylimidazol-derivate, ihre herstellung und verwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3330192 1983-08-20
DE3330192A DE3330192A1 (de) 1983-08-20 1983-08-20 4-alkylimidazol-derivate, ihre herstellung und verwendung

Publications (2)

Publication Number Publication Date
EP0139135A1 EP0139135A1 (fr) 1985-05-02
EP0139135B1 true EP0139135B1 (fr) 1987-07-08

Family

ID=6207095

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84109603A Expired EP0139135B1 (fr) 1983-08-20 1984-08-13 Dérivés d'alkyl-4-imidazole, leur préparation et leur application

Country Status (7)

Country Link
US (1) US4602927A (fr)
EP (1) EP0139135B1 (fr)
JP (1) JPS6075466A (fr)
AT (1) ATE28192T1 (fr)
CA (1) CA1231953A (fr)
DE (2) DE3330192A1 (fr)
IL (1) IL72681A (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0614890B1 (fr) * 1993-03-12 1997-09-03 Lonza AG Procédé pour la préparation de 5-chloroimidazoles facultativement substitués sur la position 2
US5484939A (en) * 1993-03-12 1996-01-16 Lonza Ltd. 2-substituted 5-chlorimidazoles
GB201401198D0 (en) * 2014-01-24 2014-03-12 Bial Portela & Ca Sa Process for the syntheis of substituted urea compounds

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996366A (en) * 1973-11-19 1976-12-07 The Boots Company Limited Thio derivatives of imidazol-1-yl carboxamides
US4187100A (en) * 1976-10-13 1980-02-05 Bayer Aktiengesellschaft 4,5-Dichloro-imidazole-1-carboxylic acid aryl esters and their use as herbicides
DE2745833C2 (de) * 1977-10-12 1986-10-16 VEB Fahlberg-List Chemische und pharmazeutische Fabriken, DDR 3013 Magdeburg Mittel zur Hemmung bzw. Regelung der Nitrifikation von Ammoniumstickstoff in Kulturböden
US4314844A (en) * 1979-01-11 1982-02-09 Rohm And Haas Company Herbicidal substituted imidazoles

Also Published As

Publication number Publication date
US4602927A (en) 1986-07-29
IL72681A0 (en) 1984-11-30
ATE28192T1 (de) 1987-07-15
JPS6075466A (ja) 1985-04-27
CA1231953A (fr) 1988-01-26
IL72681A (en) 1988-02-29
DE3330192A1 (de) 1985-03-07
EP0139135A1 (fr) 1985-05-02
DE3464602D1 (en) 1987-08-13

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